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XI ISC Notes
CHAPTER 6
S.Narayana Iyer,M.Sc,M.Phil
COLLOIDAL SOLUTIONS

Thomas Graham classified substances into crystalloids and colloids.


Substances like salt, sugar and urea which in the dissolved state readily pass
through a parchment paper or animal membrane are called crystalloids. On the
other hand, substances like glue, gelatin, albumin, starch etc. which in the
dissolved state do not pass through the parchment paper or animal membrane
are called colloids (Greek word meaning glue like).

Thomas Graham (1805-1869)


This division of substances was soon proved to be incorrect because a
crystalloid could behave as a colloid under different conditions. For example,
common salt, a typical crystalloid in an aqueous solution, behaves as a colloid
in benzene medium.Colloids, therefore, does not represent a separate class of
substances. Now it is replaced by the term colloidal state in which every
substance can be obtained by a suitable method. The nature of the substance
whether colloid or crystalloid depends upon the size of the solute particles.
When the size of solute particles is between 1 to 100nm, it behaves as a colloid.
On the other hand, if the size of solute particles is greater than 100 nm it exists
as suspension and if particle size is less than 1 nm it exists as true solution and
behaves like a crystalloid. Thus colloid is not a substance but a particular state
of the substance which depends upon size of its particles. The colloidal state is
the intermediate state between true solution and suspension.
A colloidal system is a heterogeneous two phase system. One phase consists
of dispersed particles of colloidal size and is called the dispersed phase. The
other phase is the medium in which the colloidal particles are dispersed. It is
called the dispersion medium.

Classification of Colloidal state


Depending upon whether the dispersed phase and the dispersion medium are
solids, liquids or gases, eight types of colloidal systems are possible. A gas
mixed with another gas forms a homogeneous mixture and hence is not a
colloidal system.
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Types of Colloidal Systems


Solid Solid Solid sol Some coloured glasses and gem stones
Solid Liquid Sol Paints, starch in water
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese,butter,jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Aerosol Fog,mist,cloud, insecticide sprays
Gas Solid Solid sol Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather

Colloidal systems may also be classified as lyophobic (solvent hating) and


lyophilic (solvent loving) sols. Lyophobic sols are those which cannot be
prepared easily by mixing the substance in a dispersion medium. They are
prepared by special methods.eg. Gold sol. Lyophilic sols are those which can
be prepared easily by mixing the substance in a dispersion medium. Eg. Starch
sol
Distinction between Lyophobic and Lyophilic Sols
LYOPHOBIC SOL LYOPHILIC SOL
1. They are prepared easily by direct 1. They are prepared by special
mixing methods.
2. They are reversible 2. They are irreversible.
3. They are very stable 3. They are unstable and requires
stabilizers
4. Addition of small amount of 4. Addition of small amount of
electrolyte has no effect electrolyte can cause precipitation
5. Viscosity is higher than that of the 5. Viscosity is nearly the same as that
dispersion medium of the dispersion medium
6. Surface tension is lower than that 6. Surface tension is the same as that
of the dispersion medium of the dispersion medium.

Preparation of Colloidal Solutions


Colloidal systems of lyophilic colloids can be prepared by simple treatment with
the dispersion medium. Starch, gum arabic, gelatin etc. form colloidal
dispersion by merely treating with water.
Lyophobic sols are prepared by two methods called
1. Condensations methods. and 2. Dispersion methods.
1. Condensation methods
In these methods, small ions or molecules are condensed together to form
particles of colloidal size. This may be achieved by chemical methods.
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(a) Oxidation: A colloidal solution of sulphur can be obtained by passing H2S


through an aqueous solution of sulphur dioxide.
SO2 + 2H2S → 2H2O + 3S
(b) Reduction: Colloidal solution of gold can be prepared by reducing gold
chloride solution with stannous chloride solution..
2AuCl3 + 3SnCl2 → 3SnCl4 + 2Au
(Sol)
(c) Double decomposition: Arsenious sulphide sol can be prepared by
passing H2S through a dilute solution of arsenious oxide.
As2O3 + 3H2S → As2S3 + 3H2O
(d) Exchange of solvent: Sulphur is soluble in alcohol, but less soluble in
water. When alcoholic solution of sulphur is poured into water a colloidal
solution of sulphur is obtained.
2. Dispersion Methods
In these methods large particles of the substance are broken down into
particles of colloidal dimension in the presence of dispersion medium. Since
the sols formed are highly unstable they are stabilized by adding some suitable
stabilizer.
(a) Bredigs’ arc method:
Preparation of gold sol: An electric arc is struck between two gold wires dipped
in water. The water is cooled by using ice. Due to the intense heat of the arc the
gold becomes vapour and it condenses under water to get particles of colloidal
size.

Bredigs’ arc method


(b) Peptisation: Peptisation is the process of conversion of a precipitate into
colloidal solution by the addition of an electrolyte. Ferric hydroxide sol can be
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prepared by this method. Ferric hydroxide precipitate is suspended in water. It


is shaken with a little ferric chloride solution. Reddish brown ferric hydroxide sol is
obtained. This is due to the adsorption of ferric ions (Fe3+) over ferric hydroxide
particles which cause them to disperse into solution because of electrostatic repulsion.
The electrolyte used for this purpose is called peptising agent.
Purification of Colloidal Solutions
1. Dialysis: Animal membranes or parchment paper have very small pores.
These allow small molecules and ions to pass through them but prevent the
bigger colloidal particles. The separation of a sol from the impure small
molecules and ions by using animal membrane or parchment paper is called
dialysis. The impure sol is placed in a bag of animal membrane and suspended
in a large vessel containing pure water. The water is continuously renewed. The
ions and small molecules will diffuse out of the bag. The diffusion of the
electrolyte through the membrane can be increased by the application of
electric field. The process is then called electrodialysis.
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2. Ultrafiltration: The separation of small molecules and ions from colloidal


solution can also be carried out by ultrafiltration. Colloidal particles will pass
through ordinary filter papers. But the pores of the filter paper can be made
smaller by dipping them in gelatin and then hardening them by dipping in
formaldehyde. Such filter papers are called ultrafilters. The process of
separating colloidal particles from small molecules or ions by using ultrafilters is
called ultrafiltration.
The ultrafilter is supported on a wire mesh and the impure sol is poured over it.
The electrolyte particles pass through it while the larger colloidal particles are
retained. It can be speeded up by applying pressure on the impure sol.
Properties of colloids
(1) Optical property
a) Faraday-Tyndall effect: When a strong beam of light is passed through a sol
contained in a glass vessel and placed in a dark room the path of the light
becomes visible. This is due to the scattering of light by the colloidal particles.
This phenomenon is called Faraday-Tyndall effect.

b) Ultramicroscope: Zsigmondy used Tyndall effect to set up an apparatus


known as ultramicroscope. An intense beam of light is focussed on the colloidal
solution contained in a glass vessel. The focus of the light is then observed with
a microscope at right angles to the beam. Individual colloidal particles appear
as bright spots against a dark background (dispersion medium). Under the
ultramicroscope the actual colloidal particles are not visible, but the light
scattered by them is visible Thus, ultramicroscope does not provide any
information about the size and shape of colloidal particles.
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(2) Kinetic property:


Brownian movement or Brownian motion.

On observing a sol with an ultramicroscope it is found that the colloidal particles


are always moving in a zig-zag manner. This irregular movement of colloidal
particles is called Brownian movement. It was first observed by a Botanist
Robert Brown using pollen grains in water. Hence the name Bownian
movement. Kinetic theory offers an explanation for Brownian movement. It is
due to the unequal bombardment of medium molecules on the colloidal
particles.

Robert Brown (1773–1858)


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(3) Electrical property:


a) Electrophoresis: The colloidal particles are either positively charged or
negatively charged. So if an electric field is applied the colloidal particles move
to the electrode bearing opposite charges and get deposited there. The colloidal
particles of metallic oxides, hydroxides etc are positively charged while metallic
sulphides, starch etc are negatively charged. The movement of colloidal
particles under the influence of an electric field is called electrophoresis.

The colloidal solution is placed in a U-tube fitted with platinum electrodes. On


passing an electric current, the charged colloidal particles move towards the
oppositely charged electrode. Thus, if arsenious sulphide is taken in the U-tube
its particles move towards the positive electrode.
4. Coagulation or precipitation: When an electrolyte is added to a sol the
colloidal particles are precipitated. It is called coagulation or precipitation. The
stability of a sol is due to charges on the colloidal particles. Due to similar
charges the colloidal particles are unable to combine together; if the charge on
the colloidal particles is neutralized they gather together and are precipitated.
When an electrolyte is added the charged ions of the electrolyte neutralize the
charge on the colloidal particles. So they are precipitated.
Hardy and Schultz rule: The coagulating capacity of an electrolyte depends on
the valency of its ions.” The higher the valency greater is its coagulating power”.
It is called Hardy and Schultz rule.
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In the coagulation of a negative sol, the flocculating power is in the order:


Al3+>Ba2+>Na+
Similarly, in the coagulation of a positive sol, the flocculating power is in the
order: [Fe (CN)6]4– > PO4 3– > SO4 2– > Cl–
The minimum concentration of an electrolyte in millimoles per litre required to
cause precipitation of a sol in two hours is called coagulating value. The smaller
the quantity needed, the higher will be the coagulating power of an ion.
Coagulation of lyophilic sols
There are two factors which are responsible for the stability of lyophilic sols.
These factors are the charge and solvation of the colloidal particles. When
these two factors are removed, a lyophilic sol can be coagulated. This is done
(i) by adding an electrolyte and (ii) by adding a suitable solvent. When solvents
such as alcohol and acetone are added to hydrophilic sols, the dehydration of
dispersed phase occurs. Under this condition, a small quantity of electrolyte can
bring about coagulation.
Protection of colloids The lyophobic sols are unstable but the lyophilic sols
are stable. The lyophilic sols can be protected from coagulation by the addition
of lyophilic sol. It is called protection. It is believed that the lyophilic colloidal
particles are adsorbed on the surface of lyophobic colloidal particles. This
envelope protects them from the action of electrolyte.
.Gold Number
The protective power of a lyophilic sol is measured in terms of gold number. It
was introduced by Zsigmondy. “It is the number of milligrams of protective
colloid just sufficient to prevent the precipitation of 10 mL of a red gold sol by
the addition of 1 mL of 10% sodium chloride solution. The smaller the value of
gold number greater is its protective power.
Applications of colloids
1. Food stuffs.
Milk, ice cream etc are colloidal in nature. Milk is an emulsion of fat in water
stabilized by milk protein. Ice cream is a dispersion of ice in cream.
2. Medicines. Colloidal medicines are more effective and are easily absorbed
by the body system. Eg. Argyrol a silver sol is used as an eye lotion. Cold liver
oil and skin ointments are emulsions.
3. Curdling of milk. The sugar present in milk produces lactic acid on
fermentation. Ions produced by the acid destroy the charge on the colloidal
particles present in milk which then coagulate and separate as curd. The same
effect is produced if any other acid is added to the milk.
4. Purification of water. Alum is added to impure water. Alum provides
Al3+ ions which neutralize the charge on the colloidal impurities. The colloidal
impurities settle down and pure water can be decanted off.
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5. Sewage disposal. Sewage water contains dirt which are colloidal in nature
and carry negative charge. These particles may be removed by using the
phenomenon of electrophoresis.
6. Smoke precipitation. Smoke is a colloidal solution of carbon particles
dispersed in air. Since carbon particles carry an electric charge. The charge on
the carbon particles is removed by the use of electrical precipitator. It was
devised by Cottrell. So it is called Cottrell’s precipitator.

7. Artificial rain. Artificial rain can be caused by throwing electrified sand from
an aeroplane. Moist air contains colloidal particles of water which carry charge.
Electrified sand helps to neutralize the charge on particles of water which
coagulate and the result in rainfall.
8. Blood. Blood is a colloidal solution of albuminoid substance and can be
coagulated by to clot by Al3+ or Fe3+ ions. Therefore bleeding can be stopped by
rubbing alum against the cut which coagulates the blood and seals the blood
vessels.
9. Blue colour of the sky. Colloidal dust particles along with water suspended
in air scatter blue light which reaches our eyes and the sky appears blue to us.
10. Tail of the comets. When a comet flies with very high speed it leaves
behind a tail of tiny solid particles suspended in air. These particles scatter light
forming Tyndall’s cone which looks like the tail of the comet.
11. Formation of delta. River water is a colloidal solution of clay particles
which carry negative charge. Sea water contains a number of electrolytes.
When river water strikes the sea water Na+, Mg2+ ions etc present in the
electrolytes of sea water coagulates the colloidal solution of clay which get
deposited with the formation of delta at the mouth of the river.
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12. Rubber industry. Latex is a colloidal solution of negatively charged rubber


particles dispersed in water and protected by gelatin. Rubber is obtained by
coagulation of latex.
13. Photographic plates and films. Photographic plates or films are prepared
by coating an emulsion of the light sensitive silver bromide in gelatin over glass
plates or celluloid films.

14. Cleansing action of soaps.


Soap is sodium or potassium salt of a higher fatty acid and may be represented
as RCOO–Na+ (e.g., sodium stearate CH3 (CH2)16COO–Na+, which is a major
component of many bar soaps). When dissolved in water, it dissociates into
RCOO– and Na+ ions. The RCOO– ions, however, consist of two parts — a
long hydrocarbon chain R (also called non-polar ‘tail’) which is hydrophobic
(water repelling), and a polar group COO– (also called polar-ionic ‘head’),
which is hydrophilic (water loving).

The cleansing action of soap is due to the fact that soap molecules form micelle
around the oil droplet in such a way that hydrophobic part of the stearate ions is
in the oil droplet and hydrophilic part projects out of the grease droplet like the
bristles. ((Micelles): There are some substances which at low concentrations
behave as normal strong electrolytes, but at higher concentrations exhibit
colloidal behaviour due to the formation of aggregates. The aggregated
particles thus formed are called micelles. These are also known as associated
colloids)
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Since the polar groups can interact with water, the oil droplet surrounded by
stearate ions is now pulled in water and removed from the dirty surface. Thus
soap helps in emulsification and washing away of oils and fats. The negatively
charged sheath around the globules prevents them from coming together and
forming aggregates.

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